Method and material for producing photographic color images



July 11, 1967 Filed oct. "a, 1964 METHD K. VAN POUCKE ETAL AND MATERIAL FOR PRODUCING PHOTOGRAPHIC COLOR IMAGES 2 Sheets-Sheet l ATTORNEYS July 11, 1967 R. K. VAN PoUcKE ETAL 3,330,560

METHOD AND MATERIAL FOR PRCDUCING PHOTOGRAPHIC COLOR IMAGES Filed Oct. b, 1964 2 Sheets-Sheet 2 k N n QQ INVENToRs Wwf/@2W al?, @farma/ze A a ad BY ZJ/@ageing www, M, M f www ATTORNEYS United States Patent 3,330,660 METHGD AND MATERIAL FOR PRODUCING PHOTOGRAPHIC COLOR IMAGES Raphal Karel Van Poucke, Mechlin, and Arthur Henri De Cat and Marcel Jacob Monbaliu, Mortsel-Antwerp, Belgium, assignors to Gevaert Photo-Producten N.V., Mortsel, Belgium, a Belgian company Filed Uct. 8, 1964, Ser. No. 402,652 Claims priority, application Great Britain, Oct. 10, 1963, 39,999/ 63; Sept. 28, 1964, 39,999/ 63 (revision) 7 Claims. (Cl. 96--56.5)

The present invention is a -continuation-in-part of our application Ser. No. 314,806 filed Oct. 8, 1963, now abandoned.

This invention relates to the prod-uctionnof photographic color images and to photographic materials containing magenta-formin-g color couplers of the pyrazolone type.

It is known that for the production of a photographic color image in a light-sensitive silver halide emulsion layer the exposed silver halide is developed to a silver image by means of an aromatic primary aminocompound in the presence of a color coupler, which by reaction with the oxidized developing substances forms a dye on the areas corresponding with the silver image.

In the subtractive three-color photography mostly a light-sensitive photographic color material is used comprising a red-sensitized, a green-sensitized and a bluesensitive silver halide emulsion layer, wherein on development by means of suitable color couplers, a cyan, a magenta and a yellow dye image are formed respectively.

As known distinction should be made between color couplers for negative and positive materials e.g. with respect to the absorption spectrum of the dyes to be formed.

The present invention relates to a process for the production of photographic color images by means of color couplers, which on color development with an aromatic primary amine as developing substance form a magenta dye possessing favorable spectral properties for use in negative material.

The present invention also relates to photographic materials comprising said color couplers, by means of which magenta dye images are formed which can be masked e.g. according to the principles for integral masking set forth in the U.S. patent application Ser. No. 71,117, now U.S. Patent No. 3,245,787, of Jozef Frans Willems and l an Iaeken and the U.S. patent application Ser. No. 296,942 of Jan Jaeken, Roger Alois Spriet, Hugo Vital Van Goethem and Maurice Antoine de Ramaix.

These objects are accomplished by using, in the color development of a latent image of exposed silver halide, color couplers corresponding to the general formula:

wherein:

A is a member selected from the lgroup consisting of a sulfonic acid group and a sulfonate group, e.g. an alkali metal sulfonate group or an ammonium sulfonate group;

Z represents the atoms necessary to complete an aromatic nucleus, which may be further substituted by at least one substituent e.g. a methyl group, a chlorine atom or a bromine atom;

Y is a bivalent aromatic radical e.g. a phenylene radical or a substituted bivalent aromatic radical e.g. chlorophenylene;

X is a member selected from the group consisting of a sulfur atom, a sulfonyl group, a -SOQNH- group and a substituted sulfonamide group, e.g. a -SO2N (CH3) group,

D is a radical rendering the color coupler fast to diffusion, such as an acyclic aliphatic radical comprising 5 to 20 carbon atoms.

The color couplers used according to the present invention can be prepared according to the following reaction scheme:

wherein: D, X, Y and Z have the same signicance as set forth above.

PREPARATION 1 l /N\ soN a o=o N 1 3 A suspension of 20 g. of o-sulfobenzoic anhydride and 46.3 g, (0,1 mole) of 1-(4-n-hexadecylsulfonylphenyl) 3-aminopyrazolin-5-one (prepared as described in the U.S. patent application Ser. No. 314,594) is prepared in 300 ml. of anhydrous benzene. After heating the reaction mixture for l hr. on a water bath, 200 ml. of acetonitrile is added. The whole is cooled to room temperature. The resulting precipitate is ltered oif, suspended in ethanol and treated with the theoretical quantity of 1 N sodium ethylate, to form the sodium salt of the obtained pyrazolone compound. The sodium salt is separated by ltration and dried. It is a white powder readily soluble in water.

PREPARATION 2 o,s|-NH- orr,) -0133 SOaH g. of o-sulfobenzoic anhydride and 24 g. of 1-(4-nhexadecylsulfarnoylphenyl) 3-amino-2 pyrazolin-S-one (prepared as described in the U.S. patent application Ser. No. 314,594) are suspended in 100 m1. of anhydrous benzene and heated on a boiling water bath. After heating for minutes 100 ml. of acetonitrile is added, whereupon the resulting precipitate is separated by filtration and dried.

PREPARATION 3 O 2.5- (CHr) xs-CH;

N soaNa o-C N 1-[4-(N-methyl-N-hexadecylsulfamoyl) phenyl]3(2 sulfobenzamido)-2-pyrazolin-5-one sodium salt.

(a) 4-(N-methyl-N-hexadecyl-sulfamoyl) phenylhydrazne is prepared analogously to the preparation of 4- n-hexadecylsulfamoyl-phenylhydrazine (described in the U.S. patent application Ser. No. 314,594) from 4-(N- methyl-N-hexadecylsulfamoyl)-brornobenzene and anhydrous hydrazine, by reiiuxing said reactants for hours in ethylene glycol monomethylether. Melting point: 94 C.

(b) 1-[4-(N-methyl-N-hexadecylsulfamoyl) phenyl]- 3-amino-2-pyrazolin-S-one.-42.5 g. (0.1 mole) of 4-(N- methyl-N-hexadecylsulfamoyl)-phenylhydrazine and 10.5 g. (0.1 mole) of -imino--ethoxpropionic acid ethyl ester hydrochloride are stirred for 15 min. at room temperature in 100 ml. of pyridine. The mixture is poured into 200 ml. of methyl acetate. The crystalline precipitate is then ltered and dissolved while heating in 150 ml. of ethanol. To the heated solution 70 ml. of 3 N sodium hydroxide are added and after stirring for 10 minutes, the solution is diluted with water and neutralized with acetic acid. The resulting precipitate is ltered 01T and recrystallized from isopropanol. Melting point: 127 C.

(c) 1-[4-(N-methyl-N-hexadecylsulfamoyl) phenyl]- 3-(2-Sulfobenzamido)-2-pyrazoln-5-one sodium salt.- 49.2 g. of 1-(4-N-methyl-N-hexadecylsulfamoyl)-phenyl- 3-amino-2-pyrazolin-5-one and 18.4 g. of sulfobenzoic anhydride are heated for 2 hours in 200 ml. of benzene. After adding acetonitrile and filtering, the precipitate is dissolved in water and salted out with sodium acetate. The white crystalline precipitate is recrystallized from ethanol.

PREPARATION 4 SOaH pyrazolin-S-one is obtained which after recrystallizaton from acetonitrile melts at 126 C.

By condensation of this pyrazolone compound with osulfobenzoic anhydride the color coupler having the above-mentioned formula is obtained. Melting point: 255 C.

PREPARATION 5 anhydride, the compound with the above-mentioned struc- 1-(2-chloro-4-n-hexadecylsulfonylphenyl) 3-(2-sulfotural formula is obtained as a white powder melting at 260 C.

PREPARATION 6 OzIS-(CHzin-CH:

l N SOaH Cl er i H20- C-NH-CO- PREPARATION 7 1 (2 n hexadecylthio-5-chlorophenyl)-3-(2-sulfobenzamido -2-pyrazolin-5-one.

(a) 3-amno-4-n-hexadecyllh0cl1Iorobenzene--91 g. of 3 amino-4-mercapto-chlorobenzenc, prepared according to Cassey, Sharpe and Stephens, I Chem. Soc. (1963) 4324, are dissolved in 380 ml. of 10% alcoholic potassium hydroxide. To this solution 175 g. of n-hexadecylbromide are added dropwise, whereby the temperature increases until -88 C. The solution is stirred for 1 hour and poured into water. The formed precipitate is collected by filtration and then after being dried dissolved in 2 l.`

of 30% alcoholic hydrochloric acid. A crystalline precipitate of amine hydrochloride is obtained on cooling. Melting point: 100-101 C.

(b) 2nhexadecyltho-S-phenyIhydrazne.-295 g. of 2nhexadecylthio5chloroaniline hydrochloride are dissolved inV 2900 rnl. of acetic acid and 142 ml. of concentrated hydrochloric acid. At 27 C. 125 ml. of isoamyl nitrite are added whereupon the solution is stirred for 30 minutes at 27-30 C. The obtained diazonium salt solution is added dropwise at 5 C. to a solution of 370 g. of tin(II) chloride dihydrate in 370 ml. of concentrated hydrochloric acid. After stirring the suspension for 1 hour at 10, it is heated to 65 C. until complete dissolution. Then 700 g. of ice are added.,The formed precipitate is filtered olf and dissolved in 1. 1. yof hexane. Yield: 192 g. of hydrochloride. Melting point: 107 C.

By treating this hydrochloride with the theoretic amount of alcohol potassium hydroxide while heating, the free 2-n-hexadecylthio-5-chloro phenylhydrazine is obtained. Melting point: 40 C.

(c) I-(Z-n-hexadecylthio 5 chlor0phenyl)3amno 2pyrazoIz'n-5-one.-20 g. of the prepared 2nhexa decylthio-S-chloro-phenylhydrazine are melted with l g. of lB-amino-,B-ethoxyacrylic acid ethyl ester on a water bath of 80 C. To the melt are added 3 drops of acetic acid, whereupon it is allowed to cool until room temperature. After 30 minutes 100 ml. of 5% aqueous sodium methylate are added and 15 minutes later the mixture is diluted with 100 ml. of water and acidiied with acetic acid. The precipitate formed is extracted with benzene. After evaporation of this solvent, the residue is recrystallized from isopropyl ether. Yield: l g. Melting point: 100 C.

(d) 1-(2 n-hexadecyIthi0-5-chlorophenyl)-3-(2-sulf0- benzamido)-1-pyrazolin-5-one.23 g. of the prepared l (2 n hexadecylthio 5 chlorophenyl)3amino-2 pyrazolin -5- one and 10.5 g. of o-sulfobenzoic anhydride are ydissolved in 160 ml. of benzene on a boiling water bath. After 30 minutes 100 ml. of acetonitrile are added and the formed precipitate is filtered 01T. Yield: 27 g. Melting point: above 250 C.

PREPARATION 8 SOaH 1-(2-n-octadecylthiophenyl)-3-(2 sulfobenzamido)2 pyrazolin-S-one.

This compound is prepared analogously to that of Preparation 7. Melting point: above 250 C.

The color couplers used according to the present invention, on color development form dyes possessing in respect of known l-aryl-3-acylamino-2-pyrazolin-5-ones a low side-absorption for red light. As mentioned above the color couplers according to the general formula given above are suited for the formation of an integral dye' mask-image in the developed color negative.

According to the processes described in the U.S. patent specications 3,012,884; 3,013,879 and 3,047,385 and in the U.S. patent applications Ser. Nos. 71,117 (now U.S. Patent No. 3,245,787); 100,010 (now U.S. Patent No. 3,245,788); 278,453 and 296,942, the mask images are formed in the color negative itself, hence the name integral mask images. These mask images have a gradation opposite to that of the dye images formed on color development and a light absorption in a wavelength'region wherein the dye images formed on color development have an undesirable absorption. When printing such an integrally masked color negative on a light-sensitive positive color material, spectrally right color prints are obtained, since the mask image and the proper exposure technique on printing eliminate by compensation the deleterious influence of the side-absorptions of the negative color image formed on color development.

The formation of an integral mask image according to the processes described in the mentioned U.S. patent specifications and applications is based on the suitability of determined color couplers to be coupled in an oxidizing medium such as an alkaline photographic bleaching bath with oxidatively coupling compounds also described therein. i

For instance, in order to form in a photographic material containing a 2-pyrazolin-5-one color coupler according to the above general formula an integral masking dye image, which compensates the side-absorption in the blue of the primary magenta dye image formed on development, the unaltered 2-pyrazolin-5-one color coupler on the non-exposed areas of the photographic material after color development is oxidatively coupled, eg. in the photographic bleaching bath, with a suited oxidatively coupling compound so as to form a yellow dye. In this way, in the photographic material itself a yellow mask image is formed having a gradation opposite to that of the primary magenta dye image.

The magenta forming color couplers according to the above formula usually are added to a green-sensitized silver halide emulsion. According to the most applied embodiment this silver halide emulsion is coated as the second color coupler containing layer of a multilayer photographic color material. Such a photographic multilayer color material usually consists in the indicated sequence of a support, a -red-sensitized silver halide emulsion layer containing a cyan-forming color coupler, a Igreen-sensitized silver halide emulsion layer containing a magenta-forming color coupler, a yellow filter layer mostly consisting of colloidal silver dispersed in gelatin, and a `blue-sensitive silver halide emulsion layer containing a yellow-forming color coupler.

According to a preferred embodiment applied in the production of a photographic multilayer color material, the Z-pyrazolin-S-one color coupler according to the above general formula together with an oxidatively coupling compound also named masking compound preferably an oxidatively coupling compound according to the general formula described in the U.S. patent application Ser. No. 296,942 is incorporated in a non-migratory form in the green-sensitized silver halide emulsion layer.

The support of this photographic multilayer color material may consist of paper, glass, cellulose nitrate, a cellulose ester such as cellulose triacetate, a polyester, polystyrene or another synthetic or natural resin.

In the development of exposed photographic silver halide emulsion layers, using the couplers described above, any color-forming developer containing a primary amino group may be used. These include developers having two primary amino groups as well as those having one of the amino groups substituted or having substituents in the ring such as alkylphenylene diamines. These compounds are usually used in the salt form such as the hydrochloride or the sulfate, which are more stable than the amines. All of these compounds have an unsu-bstituted amino group which enables the oxidation products of the developer to couple with the color forming compounds to form a dye.

Suitable developing substances are aromatic primary amino compounds such as p-phenylenediamine and derivatives thereof such as N,N-diethyl-Nsulfomethyl-pphenylenediamine and N,Ndiethyl-N'-carboxymethyl-p phenylenediamine.

The accompanying drawings represent the absorption curves of a dye obtained by means of a color coupler according to the general formula described above and of dyes obtained with known 3-acylamino-Z-pyrazolin-S- 7 one couplers of the type described in U.S. patent specification 2,694,718.

FIGURE 1 represents the absorption curves A and B of the dyestulfs, which are formed on development with N,Ndiethyl-p-phenylenediamine of two silver halide emulsion layers respectively containing the color couplers having the following structural formulae:

SOBNB (er if HzC- O-NH-C O- (curve A) l /N\ O=C N NH-C O- NaOaS (curve B) FIGURE 2 represents the absorption curves C and D of the dyestuffs, which are formed on development with N,N-diethyl-p-phenylenediamine of two silver halide emulsion layers respectively containing the color couplers having `the following structural formulae:

The following examples illustrate the invention,

Example 1 To 1/2 kg. of a green-sensitive silver bromo-iodide (3 mol percent iof iodide) emulsion containing 0.112 mol of silver halide is added at 45 C. 6 g. of the color coupler of preparation 1 dissolved by heating to 60 C. in a mixture of 27 ml. of ethanol, 30 ml. of distilled water and 3 ml. of 2 N aqueous sodium hydroxide. After acidilication with acetic acid to pH 6 and after addition of the usual additives such as hardeners, wetting agents, stabilizers and the necessary amount of distilled water to obtain 1 kg. of emulsion, the latter is coated at a coverage of 10 sq.m. per kg. on a cellulose triacetate support and dried. After exposure through a grey wedge with a constant 0.15, the photographic material is developed for 8 minutes at 20 C. in a color developing bath of the following composition:

N,N-diethyl-phenylenediamine hydrochloride g-- 2.75

The developed material is treated for 4 minutes in a stop bath of the following composition:

Potassium alum g-- 15 Acetic acid cm.3 10 Borax g-- 21 Wate to make l 1 The material is rinsed for 10 minutes with water and then treated in a fixing bath of the following composition:

Sodium thiosulfate-S-water g-- 200 Anhydrous potassium metabisulfite g-- 25 Potassium alum g 15 B-oric acid g 7.5 Water to make l 1 After fixing the material is treated in a bleaching bath of the following composition:

Borax g-- 22 Anhydrous potassium bromide g-- 14 Anhydrous sodium bisulite g 4 Potassium hexacyanoferrate(III) g Water to make l 1 After bleaching, the material is rinsed with water for 6 minutes and fixed for another 6 minutes in a bath with the following composition:

Anhydrous sodium hexametaphosphate g-- 1 Anhydrous sodium thiosulfate g-- Anhydrous sodium sulite g-- 10 Anhydrous sodium carbonate g-.. 6 Anhydrous sodium bicarbonate g 14 Water to make l-- 1 After a iinal rinsing the material is dried. A magenta colored wedge image is obtained having an absorption maximum at 550 mp.

Example 2 To 1/2 kg. of a green-sensitive silver bromo-iodide (3 mol percent of iodide) emulsion containing 0.115 mol of silver halide is added a mixture of a solution of 6 g. of the color coupler of Preparation 1 and a solution of 4 g. of 1 phenyl-4-methyl-2-quinolone-n-hexadecylsulfonylhydrazone, a masking compound described in the U.S. patent application Ser. No. 296,942. For that purpose the color coupler is rst dissolved in a mixture of 27 ml. of ethanol, 30 ml. of distilled Wate-r and 3 ml. of 2 N aqueous sodium hydroxide, and the mask forming compound first dissolved in a mixture of 40 cm.3 of diacetone alcohol, 9 cm.3 `of 2 N aqueous sodium hydroxide and 32 cm.3 of distilled water. After acidification with acetic acid to pH 6 and after addition of the usual ingredients such as hardeners, wetting agents, stabilizers, and the necessary amount of distilled water to obtain 1 kg. of emulsion, the latter is ready to be coated. After coating, the emulsion forms part of a multilayer photographic material comprising the following superposed layers in the indicated sequence: a support, an autihalation layer, a gelatin insulating layer, a red-sensitized silver halide emulsion layer containing a cyan-forming color coupler, a gelatin interlayer, a layer of the above mentioned green-sensitized silver halide emulsion, a yellow filter layer, a bluesensitive silver halide emulsion layer containing a yellowforming color coupled and at last a gelatin overcoat as antistress layer.

In a similar green-sensitized silver halide emulsion as described in Example 2, the color coupler is replaced by a same amount of the color coupler of preparation 3 dissolved in a mixture of 28 cm.3 of distilled water and 12 cm.3 of ethanol. The emulsion is coated and processed as described in Example 2. Iu the greensensitized silver halide emulsion layer a negative magenta colored image is obtained together with a yellow dye mask image being of opposite gradation to that of the magenta dye image and reducing in the printing process the disturbing influence of the side-absorption in the blue of the primarily formed magenta dye image.

Example 4 To 1/2 kg. of a green-sensitive silver bromo-iodide (3 mol percent of iodide) emulsion containing 0.112 mol of silver halide is added at 45 C. 6 g. of the color coupler of Preparation 8 dissolved in a mixture of 12 ccs. of 1 N ethanolic potassium hydroxide and 108 ccs. 0f distilled water. After acidification with acetic acid to pH 6 and after `addition of the usual additives such as hardeners, wetting agents, stabilizers andthe necessary .amount of distilled water to obtain 1 kg. of emulsion, the latter is coated at a coverage of 10 sqm. per kg. on a cellulose triacet-ate support and dried. After exposure through a grey wedge with a constant 0.15, the photographic material is developed and further treated as described in Example l.

A magenta colored wedge image is obtained having an absorption maximum at 540 ma.

We claim:

1. A method of producing a magenta colored 'photographic image in a silver halide emulsion layer, which comprises exposing the layer and developing it in the presence of a coupler compound having the following general formula:

wherein A is a member selected from the group consisting of sulfonic acid group and a sulfonate group,

Z represents the atoms necessary to complete an aromatic nucleus,

Y is a bivalent'4 aromatic radical,

X is a member selected from the group consisting of sulfur, sulfonyl, SO2NH yand -S O n-N- and D is an acyclic aliphatic radical comprising to 20 carbon atoms.

2. A method of producing a magenta colored photographic image in a silver halide emulsion layer, which comprises exposing the layer and developing it While containing a coupler compound having the following gen` eral formula:

wherein:

A is a member selected from the group consisting of sulfonic acid and sulfonate,

Z represents the atoms necessary to complete an aromatic nucleus,

X is a member selected from the fur, sulfonyl, -SO2NH- and group consisting of sul- O i z-a-x-e O wherein:

so Y

group consisting of and D is an acyclic aliphatic radical comprising 5 to 20 carbon atoms. 4. A photographic element containing at least one silver halide emulsion layer and a coupler compound havv ing the 4following general formula:

wherein A is a member selected from the group consisting of sulfonic acid group and a sulfonate group,

Z represents the atoms necessary to complete an aromatic nucleus,

Y is a bivalent aromatic radical,

l l l 2 X is a member selected from the group consisting of sul- Y is abivalent aromatic radical,

fur, sullonyl, -SOZNH- and X is a member selected from the group consisting of SO, N sulfur, sulfonyl, -SO2NH and CH3 5 Soi-N and CH3 D is an acyclic aliphatic radical comprising 5 to 20 carand bon atoms. D is an acyclic aliphatic radical comprising 5 to 20 car- S. A photographic element containing at least one silbon atoms, and an oxidatively coupling compound corJ ver halide emulsion layer, which contains a coupler corn- O responding to the following general formula: pound for magenta having the following general formula: R',

D t i l,- N-NH-R'l X ZI if l1 A |l @#C/ \N o R I "g wherein: H -NH C-C C C H l,I R1 is a labile functional substituent adapted to besplit 0 Z off by said oxidizing treatment, wherein: R'z and R'3 are :selected from the glass consisting of an A is a member selected from the group consisting of sulalkyl radical, an aryl radical and an aralkyl radical,

onic acid group and a sulfonate group, and Z represents the atoms necessary to complete an aromatic Z represents the non-metallic atoms necessary to close nucleus, an aromatic nucleus of the benzene series. Yisabivalent aromatic radical, 7. A photographic element containing at least one X is a member selected from the group consisting of sulgreen-sensitized silver halide emulsion layer comprising fur, sulfonyl, -SO2NH and as coupler compound for magenta the compound having SO: N the following structure:

CH2 O2S-(CH2)is-CH;

and D is an acyclic aliphatic radical comprising 5 to 20 carbon atoms, and an oxidatively coupling compound, which on the oxidizing treatment of the photographic element in the /N\ SCENE bleaching bath oxidatively couples with the said coupler O=C N compound for magenta to form a dye absorbing in at least one region of the side-absorptions of the magenta dye, which is formed with the said coupler compound for and as masking compound the compound having the folmagenta in the color deevlopment of the photographic lowing structure: element with a primary aromatic amino developing agent. CH 6. A photographic element according to claim 5 conl 3 taining at least one green-sensitized silver halide emulsion 4D layer, which contains a coupler compound for magenta having the following general formula: N NH so: (CH) CH 21h'- 3 1l) If )IC i N A 0%/ l n References Cited H2O- CTNH-" 5 UNITED STATES PATENTS Z 2,353,205 7/1944 Vinum etai 96-100 wherein: 2,369,489 2/ 1945 Porter et al. 96-100 A is a member selected from the group consisting of 3,245,787 4/1966 Willems et al- 96-9 sulfonic acid group and a sulfonate group, h Z represents the atoms necessary to complete an aromatic NORMAN G' TORCHIN Prmary Examiner' nucleus, J. TRAVIS BROWN, Assistant Examiner. 

1. A METHOD OF PRODUCING A MAGENTA COLORED PHOTOGRAPHIC IMAGE IN A SILVER HALIDE EMULSION LAYER, WHICH COMPRISES EXPOSING THE LAYER AND DEVELOPING IT IN THE PRESENCE OF A COUPLER COMPOUND HAVING THE FOLLOWING GENERAL FORMULA: 